CN106513055B - A kind of PDMS-TiO2-SiO2The preparation method of film and its application in fixed bed light degradation reactor - Google Patents
A kind of PDMS-TiO2-SiO2The preparation method of film and its application in fixed bed light degradation reactor Download PDFInfo
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- 238000006731 degradation reaction Methods 0.000 title claims abstract description 46
- 230000015556 catabolic process Effects 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 229910003082 TiO2-SiO2 Inorganic materials 0.000 claims abstract description 61
- 238000003760 magnetic stirring Methods 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000003756 stirring Methods 0.000 claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 26
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 17
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 17
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 17
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 17
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 12
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 62
- 229910052740 iodine Inorganic materials 0.000 claims description 62
- 239000011630 iodine Substances 0.000 claims description 62
- 239000004575 stone Substances 0.000 claims description 33
- 238000002156 mixing Methods 0.000 claims description 25
- 239000002131 composite material Substances 0.000 claims description 22
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 19
- 238000002604 ultrasonography Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 238000002474 experimental method Methods 0.000 claims description 13
- 239000011521 glass Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 230000001376 precipitating effect Effects 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 240000001414 Eucalyptus viminalis Species 0.000 claims description 8
- 239000003755 preservative agent Substances 0.000 claims description 8
- 230000002335 preservative effect Effects 0.000 claims description 8
- 239000003365 glass fiber Substances 0.000 claims description 7
- 238000000338 in vitro Methods 0.000 claims description 7
- 238000007711 solidification Methods 0.000 claims description 6
- 230000008023 solidification Effects 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 5
- 238000002242 deionisation method Methods 0.000 claims 1
- 238000004062 sedimentation Methods 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 40
- 239000002351 wastewater Substances 0.000 abstract description 11
- 239000002904 solvent Substances 0.000 abstract description 8
- 238000005336 cracking Methods 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 7
- 239000002105 nanoparticle Substances 0.000 abstract description 5
- 239000010409 thin film Substances 0.000 abstract description 5
- 238000003980 solgel method Methods 0.000 abstract description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 229920005573 silicon-containing polymer Polymers 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 2
- 239000010919 dye waste Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 230000031700 light absorption Effects 0.000 abstract 1
- 230000005855 radiation Effects 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 21
- 230000001699 photocatalysis Effects 0.000 description 16
- 238000007146 photocatalysis Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 8
- 238000012545 processing Methods 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- 239000011941 photocatalyst Substances 0.000 description 6
- 238000010828 elution Methods 0.000 description 5
- 229960004756 ethanol Drugs 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 229910021642 ultra pure water Inorganic materials 0.000 description 5
- 239000012498 ultrapure water Substances 0.000 description 5
- 239000000969 carrier Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 2
- -1 silicon alkoxide Chemical class 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
A kind of PDMS-TiO2‑SiO2The preparation method of film and its application in fixed bed light degradation reactor, using tetraethyl orthosilicate as raw material, ethanol as solvent, phosphoric acid is catalyst, and adds TiO2Nanoparticle and dimethyl silicone polymer with elastic group, are obtained using sol-gel method and normal pressure freeze-day with constant temperature technology.The light degradation reactor body is by bracket, fluorescent tube, flowmeter, temperature control magnetic stirring apparatus, circulating pump, reservoir and PDMS-TiO2‑SiO2The composition such as thin-film carrier.The stirring light degradation of traditional dispersion liquid is changed into fixed bed film reactor form by the present invention, overcomes TiO2Molecule is easy to run off, and the separation with waste water is slowly and expensive, the PDMS-TiO that suspended particles stop a series of problems, such as influencing the radiation depth of light on the absorption of light, while preparing2‑SiO2Film is strong without cracking, hydrophobicity, can effectively handle organic dye waste water.
Description
Technical field
The invention belongs to field of environment engineering technology, are related to a kind of photochemical catalyst preparation method for treatment of Organic Wastewater
And the application in fixed bed light degradation reactor.
Background technique
With the continuous discharge of the industrial wastewaters such as Dyestuff synthesis, printing and dyeing and continuing on for various dyestuffs, into environment
Dye quantity and type are continuously increased, and environmental pollution caused by dyestuff is on the rise.According to statistics, about 15% dyestuff of the whole world exists
It is discharged into waste water in production process.These waste water from dyestuff have the characteristics that water is big, coloration is deep, high COD, high BOD, are to pass
Biology, biochemistry, the physical chemistry method of system are difficult to a kind of industrial wastewater of degradation treatment.Photocatalysis technology is as a kind of advanced oxidation mistake
Journey technology is counted as high temperature and incinerates method, improves the conventional treatment methods such as activated sludge process, anaerobic digestion and other physical chemistry
Reasonable, effective supplement.Semiconductor material (such as TiO that photocatalysis technology uses2) why can be used as photochemical catalyst
Redox reaction is participated in, is determined by the electronic structure of itself.TiO2Photocatalysis can effective degradation of dye waste water, make dirt
Dye object mineralising is CO2, water and other small-molecule substances: use TiO2Photocatalytic degradation is with nontoxic, quick, operating cost is low, catalysis
The advantages that agent is cheap and easy to get, without secondary pollution, therefore have a extensive future.But it handles waste water and mostly uses suspended dispersed method greatly,
TiO2Molecule is easy to run off, and the separation with waste water is slowly and expensive, and suspended particles affect light to the absorption blocking of light
Radiate depth.Moreover, the concentration for certain harmful intermediate products that the organic matter of processing and degradation generate is lower, with suspension TiO2
Particle contact frequency is not high, causes mineralization of organic material speed small, influences catalytic degradation effect.Therefore, it is studied in photocatalysis technology
In generally select other materials to TiO2It is loaded or is modified to improve its photocatalysis performance.To prevent TiO2The cracking of coating,
It falls off, it can be TiO2Particle is fixed to SiO2On equal carriers, and by TiO2Particle is embedded into meso-porous titanium dioxide silicon substrate can also be into
The catalytic activity of one step raising titanium dioxide.Currently used method is colloid TiO2Particle and silicon alkoxide (such as ethyl orthosilicate
Alcosol) mixing.But ethyl orthosilicate is easy to crack in hydrolysis, the silica dioxide gel formed in drying process, thus easily from
It falls off on carrier.Present invention seek to address that this problem, specific practice is the introducing elastic material such as end group in silanol salt sol
It is modified for the dimethyl silicone polymer (PDMS-OH) of hydroxyl, increases flexible, inhibition capillary pressure, effectively prevention titanium dioxide
Silicon thin film falls off from carrier surface.
Summary of the invention
The purpose of the present invention is to propose to one kind to be based on PDMS-TiO2-SiO2The preparation method of film and its fixed bed light drop
Solve the application in reactor.
The present invention is by TiO2Nanoparticle passes through the SiO that obtains with sol-gel method2Gel progress is compound, is made without cracking
PDMS-TiO2-SiO2Composite photocatalyst material, and be supported on the carriers such as float stone, glass fibre and medical stone and formed
PDMS-TiO2-SiO2Film.Composite photo-catalyst not only solves TiO2Recycling during nanoparticle light-catalyzed reaction is asked
Topic, moreover, TiO can solved by having the introducing of the dimethyl silicone polymer (PDMS-OH) of elastic group2Photochemical catalyst is fixed
While change, its specific surface area, thermal stability and frame strength etc. are further increased, and the hydrophobic of composite catalyst can be improved
Performance, to achieve the purpose that improve photocatalyst activity.
The present invention is achieved by the following technical solutions.
One kind being based on PDMS-TiO2-SiO2The preparation method of film, with tetraethyl orthosilicate (TEOS) for raw material, anhydrous second
Alcohol makees solvent, and phosphoric acid adds TiO as catalyst2Nanoparticle (P25) and the polydimethylsiloxanes with elastic group
Alkane, using sol-gel method and the preparation of normal pressure freeze-day with constant temperature technology without cracking PDMS-TiO2-SiO2Gel.It is with float stone simultaneously
Carrier is prepared for a kind of based on PDMS-TiO with dip coating2-SiO2Film, steps are as follows for specific preparation method:
(1) pretreatment of substrate: the base materials such as float stone, glass fibre and medical stone are cleaned by ultrasonic completely, and in 60
It is dried in DEG C baking oven.
(2) TiO 2 particles are weighed in iodine flask, then pipette mixed in dehydrated alcohol to iodine flask, iodine flask
It is placed on magnetic stirring apparatus, opens magnetic stirring apparatus, pipette ethyl orthosilicate, under rapid stirring, be added dropwise
Into iodine flask, it is placed on magnetic stirring apparatus and stirs.
(3) deionized water is added dropwise in iodine flask under rapid mixing conditions, is placed on magnetic stirring apparatus and stirs.
(4) iodine flask is placed in ultrasonic cleaner and carries out ultrasound, pass through top water inlet and bottom in ultrasonic procedure
Water temperature, water level in water management washer out, keep constant.
(5) after ultrasound, PDMS-OH is added dropwise in iodine flask under rapid mixing conditions, magnetic force is placed in and stirs
It mixes and is stirred on device.
(6) catalyst phosphoric acid is added in a manner of being added dropwise to be stirred, obtains PDMS-TiO2-SiO2Colloidal sol.
(7) by PDMS-TiO2-SiO2Colloidal sol is sealed after being placed in container with preservative film, places into warp in constant temperature and humidity drying case
After reaction precipitating, bottom white gum substance, i.e. PDMS-TiO are obtained2-SiO2Composite material.
(8) experiment in vitro is prepared into PDMS-TiO2-SiO2Composite material is applied on the substrates such as float stone, certain interval of time
It smears second, aforesaid operations smear certain number repeatedly, and are evenly distributed in glass support plate, and being put into constant temperature and humidity makes
Its colloidal sol solidifies a period of time to get PDMS-TiO is arrived2-SiO2Film.
In the step (2), the form of TiO 2 particles are as follows: anatase titanium dioxide: 70-80%, rutile-type: 20-30%.
In the step (2), the ratio of TiO 2 particles and dehydrated alcohol is 1:40-50g/mL, titanium dioxide grain
The ratio of son and ethyl orthosilicate is 1:10-15g/mL；Mixing time is 2-3h.
In the step (3), the ratio of TiO 2 particles and deionized water is 1:6.4-10g/mL, and mixing time is
10-30min。
In the step (4), ultrasonic time 10-30min, water temperature is 25-30 DEG C in ultrasonic cleaner.
In the step (5), the ratio of TiO 2 particles and PDMS-OH are 1:8-12g/mL, mixing time 10-
30min。
In the step (6), the ratio of TiO 2 particles and phosphoric acid is 1:6-10g/mL, mixing time 10-
30min。
In the step (7), constant temperature and humidity drying case imposes a condition are as follows: humidity 60%, 25-30 DEG C of temperature；Reaction precipitating
Time is 48-72h.
In the step (8), interval time 24-36h, curing time 7-9d, smearing number is 3-4 times, is smeared
TiO2Gross mass is 4500mg.
Light degradation reactor of the present invention includes bracket (5), ultraviolet lamp tube (6), spinner flowmeter (7), circulating pump
(3), reservoir (4) and PDMS-TiO2-SiO2Film (1).Reaction unit schematic diagram simulates dyestuff Acid Orange II as shown in Figure 1:
Waste water (V=1500mL, C=20mg L-1) on the basis of this reaction unit it is placed in glass container, pass through temperature control magnetic stirring apparatus
(8) it is stirred uniformly, and the temperature of solution is adjusted, then pass through after circulating pump is promoted to certain altitude, pass through
The spinner flowmeter (7) for setting flow, which is flowed into, is equipped with PDMS-TiO2-SiO2In the reservoir (4) of the reactor of film (1),
Dye molecule in reservoir (4) is adsorbed degradation under catalyst and ultraviolet light, and undegradable dye molecule is flow back into
In glass container, the circulation degradation of waste water from dyestuff is then realized.Solution temperature, pH, flow velocity and carrier type etc. have been investigated in experiment
The influence of parameter degrading waste water
PDMS-TiO2-SiO2Application of the film in fixed bed light degradation reactor is as follows:
(1) select float stone as carrier, solution flow velocity is 250 mLmin-1, temperature is 35 DEG C, and experiment compares solution
PDMS-TiO in the case of five kinds of pH that pH value is 4.0,5.5,7.0,8.5,10.02-SiO2The effect of film degradation AO7, obtains pH
Good catalytic effect is shown under=4.0 acid condition；
(2) select float stone as carrier, solution flow velocity is 250 mLmin-1, pH value 4.0, experiment compares temperature and is
35 DEG C, 40 DEG C, PDMS-TiO under 45 DEG C of three kinds of temperature conditions2-SiO2The effect of film degradation AO7, obtaining solution water temperature is 35
DEG C the case where be better than 40 DEG C, 45 DEG C；
(3) select float stone as carrier, temperature is 35 DEG C, pH value 4.0, and it is 10 mL that experiment, which compares solution flow velocity,
min-1、70mL·min-1、130mL·min-1、190mL·min-1、250 mL·min-1PDMS-TiO under five kinds of flow conditions2-
SiO2The effect of thin-film carrier degradation AO7 obtains solution flow velocity to AO7 degradation effect sequence by well to poor for 250mLmin-1>
190mL·min-1>130mL·min-1>70mL·min-1>10 mL·min-1；
(4) solution flow velocity is 250 mLmin-1, temperature is 35 DEG C, and pH value 4.0, experiment compares float stone, glass fibers
Three kinds of carrier type PDMS-TiO of peacekeeping medical stone2-SiO2The effect of film degradation AO7 finds natural pumice compared to medical stone
Ball and glass fibre have preferably degradation and decolorizing effect.Photo catalysis reactor of the float stone as carrier, for AO7 after 12h
Dye solution degradation efficiency can reach 99.1%.
(5) select float stone as carrier, solution flow velocity is 250mLmin-1, temperature is 35 DEG C, pH value 4.0, PDMS-
TiO2-SiO2Film remains to reach 90% or more after being recycled 5 times to the degradation efficiency of AO7 dye solution, shows that this experiment is ground
The PDMS-TiO studied carefully2-SiO2Film photocatalytic material has good photocatalytic activity and stability, is film photocatalyst
Commercialization and practice provide preferable theoretical foundation.
Compared with prior art, outstanding advantages of the invention are:
1) turn conventional suspension dispersion liquid stirring light degradation form to change into fixed bed film reactor form, realize
The continuous flowing of machine waste water from dyestuff is degraded, and TiO is overcome2Recycling problem during nanoparticle light-catalyzed reaction, can be direct
Obtain the mobile phase without dyestuff and catalyst.
2) PDMS-TiO that the present invention makes2-SiO2Cracking phenomena is not present in film, not only catalytic activity with higher,
And last a long time, property is stablized, and can be used repeatedly.With the increase that number is recycled, in the identical reaction time
Interior, there is not apparent difference in the degradation situation of AO7 solution concentration, and degradation efficiency remains to reach 90% or more, illustrates PDMS-
TiO2-SiO2Is there is not the case where decline by the increase that number is recycled in film photocatalytic activity, and shows TiO2Particle is not
It is easy to fall off.
3) its production process of fixed bed film reactor is simple, low in cost, without secondary pollution and superior performance, it can be achieved that
The batch processing of dyeing waste water.
Detailed description of the invention
Fig. 1 is the Experimental equipment for the fixed bed light degradation reactor that the present invention implements preparation.Wherein, 1 is PDMS-
TiO2-SiO2Thin-film carrier, 2 be processing dye solution, and 3 be circulating pump, and 4 be reservoir, and 5 be bracket, and 6 be ultraviolet lamp tube, and 7 are
Spinner flowmeter, 8 be temperature control magnetic stirring apparatus.
Fig. 2 is PDMS-TiO in the embodiment of the present invention 12-SiO2Handle the static contact angle measurement chart before and after float stone.Wherein,
(a) it is the static contact angle measurement chart before processing, is (b) treated static contact angle measurement chart.
Fig. 3 is that float stone passes through PDMS-TiO in the embodiment of the present invention 12-SiO2The SEM figure of composite material before and after the processing.(a)
For the SEM figure before processing, (b) for treated, SEM schemes.
Fig. 4 is influence of the solution ph to degradation rate constant in the embodiment of the present invention 2.
Fig. 5 is the influence that solution water temperature degrades to AO7 in the embodiment of the present invention 3.
Fig. 6 is influence of the solution flow velocity to AO7 degradation efficiency in the embodiment of the present invention 4.
Fig. 7 is influence of 5 different carriers of the embodiment of the present invention to AO7 degradation efficiency.
Fig. 8 is the influence that cycle-index degrades to AO7 in the embodiment of the present invention 6.
Specific embodiment
Below in conjunction with the specific embodiment content that the present invention is furture elucidated.
The present invention uses sol-gel process, and preparation is without cracking PDMS-TiO under room temperature Constant pressure drying2-SiO2Gel.
Simultaneously using float stone, glass fibre and medical stone etc. as substrate, it is prepared for dip coating a kind of based on PDMS-TiO2-SiO2It is thin
Film, and investigated its application in fixed bed light degradation reactor.Fixed bed light degradation reactor assembly as shown in Figure 1, by
Glass support plate (25 × 18cm), water distributor, circulating pump, glass container (35 × 30 × 3.5cm), glass beaker, spinner flowmeter,
The composition such as magnetic force temperature control blender, stirrer.In experimentation, entire experimental provision is placed on one without other light sources not
It becomes rusty in steel container, other light is avoided to interfere.
Embodiment 1.
(1) 500mg TiO 2 particles are weighed in iodine flask, then are pipetted in 20.00mL dehydrated alcohol to iodine flask, iodine
Measuring bottle is placed on magnetic stirring apparatus, is opened magnetic stirring apparatus, 5.00mL ethyl orthosilicate is pipetted, in the condition quickly stirred
Under, it is added dropwise in iodine flask, is placed on magnetic stirring apparatus and stirs 2h；
(2) after stirring, 3.20mL deionized water is pipetted, is added dropwise in iodine flask, is placed under rapid mixing conditions
10min is stirred on magnetic stirring apparatus；
(3) will iodine flask be placed in ultrasonic cleaner in carry out ultrasound 10min, in ultrasonic procedure by top intake and
Bottom goes out water temperature in water management washer (about 25 DEG C), water level, keeps constant as far as possible；
(4) after ultrasound, 4.00mLPDMS-OH is pipetted, is added dropwise in iodine flask, sets under rapid mixing conditions
In stirring 10min on magnetic stirring apparatus；
(5) iodine flask is placed on magnetic stirring apparatus and is stirred, catalyst phosphoric acid is equally added in a manner of being added dropwise and stirs
10min is mixed, i.e. completion PDMS-TiO2-SiO2The preparation of colloidal sol；
(6) by PDMS-TiO2-SiO2Colloidal sol is sealed after being placed in 100mL beaker with preservative film to slow down the evaporation of its solvent,
It places into constant temperature and humidity drying case (humidity 60%, 25 DEG C of temperature) after reacted precipitating 72h, obtains bottom white gum substance, i.e.,
Complete PDMS-TiO2-SiO2The preparation of composite material.With brush PDMS-TiO2-SiO2It is painted on float stone.Between smear every two days
Second, aforesaid operations smear (TiO three times repeatedly2Gross mass is 4500mg), and be evenly distributed in glass support plate, it puts
Enter to make in constant temperature and humidity its colloidal sol to solidify 7.4d, i.e. completion PDMS-TiO2-SiO2The preparation of film.
In order to macroscopically preferably embody PDMS-TiO2-SiO2Composite material used on float stone after hydrophobicity
Can, the test of contact angle is carried out, test results are shown in figure 2.
In order to preferably observe PDMS-TiO2-SiO2Without cracking nanocomposite to different carriers surface shape before and after the processing
The variation of looks, to PDMS-TiO2-SiO2Colloidal sol carries out electron-microscope scanning to the surface topography before and after float stone vehicle treated, as a result as schemed
Shown in 3.
Embodiment 2.
(1) 500mg TiO 2 particles are weighed in iodine flask, then are pipetted in 21.00mL dehydrated alcohol to iodine flask, iodine
Measuring bottle is placed on magnetic stirring apparatus, is opened magnetic stirring apparatus, 4.50mL ethyl orthosilicate is pipetted, in the condition quickly stirred
Under, it is added dropwise in iodine flask, is placed on magnetic stirring apparatus and stirs 2.2h；
(2) after stirring, 3.6mL deionized water is pipetted, is added dropwise in iodine flask under rapid mixing conditions, is placed in magnetic
14min is stirred on power blender；
(3) will iodine flask be placed in ultrasonic cleaner in carry out ultrasound 14min, in ultrasonic procedure by top intake and
Bottom goes out water temperature in water management washer (about 26 DEG C), water level, keeps constant as far as possible；
(4) after ultrasound, 4.4mLPDMS-OH is pipetted, is added dropwise in iodine flask, sets under rapid mixing conditions
In stirring 14min on magnetic stirring apparatus；
(5) iodine flask is placed on magnetic stirring apparatus and is stirred, the stirring of 3.4mL phosphoric acid is equally added in a manner of being added dropwise
14min, i.e. completion PDMS-TiO2-SiO2The preparation of colloidal sol；
(6) by PDMS-TiO2-SiO2Colloidal sol is sealed after being placed in a beaker with preservative film to slow down the evaporation of its solvent, is placed into
In constant temperature and humidity drying case (humidity 60%, 26 DEG C of temperature) after reacted precipitating 53h, bottom white gum substance is obtained, that is, is completed
PDMS-TiO2-SiO2The preparation of composite material.
(7) experiment in vitro is prepared into PDMS-TiO2-SiO2Composite material is uniformly applied on float stone, smears every two days
Secondary, aforesaid operations smear (TiO three times repeatedly2Gross mass is 4500mg), and be evenly distributed in glass support plate, it is put into
Its colloidal sol is set to solidify 7d in constant temperature and humidity, i.e. completion PDMS-TiO2-SiO2The preparation of film.It is taken out after the completion of solidification, before use
It is ultrasonic half an hour, clean with ethyl alcohol and ultrapure water elution later, it is spare to be placed in 60 DEG C of drying in oven.Start photocatalysis it
Before, make catalyst dark treatment 1h in dye solution, reaches adsorption equilibrium.Ultraviolet lamp is opened, the AO7 solution of 20mg/L is made
Cycle through PDMS-TiO2-SiO2Film light degradation reaction device utilizes the NaOH or HNO of 0.1mol/L in the photocatalytic process3
It adjusts pH value of solution and is allowed to respectively 4,5.5,6.5,7,8.5,10, to probe into influence of the pH value to AO7 solution concentration, as a result as schemed
Shown in 4, during dye solution light degradation when pH=4, reaction system obtains best degradation efficiency.
Embodiment 3.
(1) 500mg TiO 2 particles are weighed in iodine flask, then are pipetted in 22.00mL dehydrated alcohol to iodine flask, iodine
Measuring bottle is placed on magnetic stirring apparatus, is opened magnetic stirring apparatus, 5.00mL ethyl orthosilicate is pipetted, in the condition quickly stirred
Under, it is added dropwise in iodine flask, is placed on magnetic stirring apparatus and stirs 2.4h；
(2) after stirring, 4.00mL deionized water is pipetted, is added dropwise in iodine flask, is placed under rapid mixing conditions
18min is stirred on magnetic stirring apparatus；
(3) will iodine flask be placed in ultrasonic cleaner in carry out ultrasound 18min, in ultrasonic procedure by top intake and
Bottom goes out water temperature in water management washer (about 27 DEG C), water level, keeps constant as far as possible；
(4) after ultrasound, 4.8mLPDMS-OH is pipetted, is added dropwise in iodine flask, sets under rapid mixing conditions
In stirring 18min on magnetic stirring apparatus；
(5) iodine flask is placed on magnetic stirring apparatus and is stirred, the stirring of 3.8mL phosphoric acid is equally added in a manner of being added dropwise
18min, i.e. completion PDMS-TiO2-SiO2The preparation of colloidal sol；
(6) by PDMS-TiO2-SiO2Colloidal sol is sealed after being placed in a beaker with preservative film to slow down the evaporation of its solvent, is placed into
In constant temperature and humidity drying case (humidity 60%, 27 DEG C of temperature) after reacted precipitating 58h, bottom white gum substance is obtained, that is, is completed
PDMS-TiO2-SiO2The preparation of composite material.
(7) experiment in vitro is prepared into PDMS-TiO2-SiO2Composite material is uniformly brushed on float stone, smears every two days
Secondary, aforesaid operations smear (TiO three times repeatedly2Gross mass is 4500mg), and be evenly distributed in glass support plate, it is put into
Its colloidal sol is set to solidify 7.4d in constant temperature and humidity, i.e. completion PDMS-TiO2-SiO2The preparation of film.It takes out, uses after the completion of solidification
It is preceding ultrasound half an hour, clean with ethyl alcohol and ultrapure water elution later, it is spare to be placed in 60 DEG C of drying in oven.Start photocatalysis it
Before, make catalyst dark treatment 1h in dye solution, reaches adsorption equilibrium.Ultraviolet lamp is opened, the AO7 solution of 20mg/L is made
Cycle through PDMS-TiO2-SiO2Film light degradation reaction device is allowed to distinguish using magnetic force temperature control blender control solution temperature
For 35 DEG C, 40 DEG C, 45 DEG C, to probe into influence of the solution temperature to AO7 solution concentration, as a result as shown in figure 5, being in solution temperature
At 35 DEG C, reaction system obtains best degradation efficiency.
Embodiment 4.
(1) 500mg TiO 2 particles are weighed in iodine flask, then are pipetted in 23.00mL dehydrated alcohol to iodine flask, iodine
Measuring bottle is placed on magnetic stirring apparatus, is opened magnetic stirring apparatus, 5.50mL ethyl orthosilicate is pipetted, in the condition quickly stirred
Under, it is added dropwise in iodine flask, is placed on magnetic stirring apparatus and stirs 2.6h；
(2) after stirring, 4.40mL deionized water is pipetted, is added dropwise in iodine flask, is placed under rapid mixing conditions
22min is stirred on magnetic stirring apparatus；
(3) will iodine flask be placed in ultrasonic cleaner in carry out ultrasound 22min, in ultrasonic procedure by top intake and
Bottom goes out water temperature in water management washer (about 28 DEG C), water level, keeps constant as far as possible；
(4) after ultrasound, 5.20mLPDMS-OH is pipetted, is added dropwise in iodine flask, sets under rapid mixing conditions
In stirring 22min on magnetic stirring apparatus；
(5) iodine flask is placed on magnetic stirring apparatus and is stirred, the stirring of 4.2mL phosphoric acid is equally added in a manner of being added dropwise
22min, i.e. completion PDMS-TiO2-SiO2The preparation of colloidal sol；
(6) by PDMS-TiO2-SiO2Colloidal sol is sealed after being placed in a beaker with preservative film to slow down the evaporation of its solvent, is placed into
In constant temperature and humidity drying case (humidity 60%, 28 DEG C of temperature) after reacted precipitating 63h, bottom white gum substance is obtained, that is, is completed
PDMS-TiO2-SiO2The preparation of composite material.
(7) experiment in vitro is prepared into PDMS-TiO2-SiO2Composite material is uniformly applied on float stone, smears every two days
Secondary, aforesaid operations smear (TiO three times repeatedly2Gross mass is 4500mg), and be evenly distributed in glass support plate, it is put into
Its colloidal sol is set to solidify 7.8d in constant temperature and humidity, i.e. completion PDMS-TiO2-SiO2The preparation of film.It takes out, uses after the completion of solidification
It is preceding ultrasound half an hour, clean with ethyl alcohol and ultrapure water elution later, it is spare to be placed in drying in oven.Before starting photocatalysis,
Make catalyst dark treatment 1h in dye solution, reaches adsorption equilibrium.Ultraviolet lamp is opened, the AO7 solution of 20mg/L is followed
Ring passes through PDMS-TiO2-SiO2Film light degradation reaction device, using spinner flowmeter change reaction unit flow velocity be allowed to be respectively
10mL·min-1、70mL·min-1、130mL·min-1、190mL·min-1、250mL·min-1, molten to AO7 to probe into flow velocity
The influence of liquid degradation efficiency, as a result as shown in fig. 6, being 250 mLmin in flow velocity-1When, reaction system obtains best degradation
Efficiency.
Embodiment 5.
(1) 500mg TiO 2 particles are weighed in iodine flask, then are pipetted in 24.00mL dehydrated alcohol to iodine flask, iodine
Measuring bottle is placed on magnetic stirring apparatus, is opened magnetic stirring apparatus, 6.50mL ethyl orthosilicate is pipetted, in the condition quickly stirred
Under, it is added dropwise in iodine flask, is placed on magnetic stirring apparatus and stirs 2.8h；
(2) after stirring, 4.80mL deionized water is pipetted, is added dropwise in iodine flask, is placed under rapid mixing conditions
26min is stirred on magnetic stirring apparatus；
(3) will iodine flask be placed in ultrasonic cleaner in carry out ultrasound 26min, in ultrasonic procedure by top intake and
Bottom goes out water temperature in water management washer (about 29 DEG C), water level, keeps constant as far as possible；
(4) after ultrasound, 5.60mLPDMS-OH is pipetted, is added dropwise in iodine flask, sets under rapid mixing conditions
In stirring 26min on magnetic stirring apparatus；
(5) iodine flask is placed on magnetic stirring apparatus and is stirred, the stirring of 4.6mL phosphoric acid is equally added in a manner of being added dropwise
26min, i.e. completion PDMS-TiO2-SiO2The preparation of colloidal sol；
(6) by PDMS-TiO2-SiO2Colloidal sol is sealed after being placed in a beaker with preservative film to slow down the evaporation of its solvent, is placed into
In constant temperature and humidity drying case (humidity 60%, 29 DEG C of temperature) after reacted precipitating 68h, bottom white gum substance is obtained, that is, is completed
PDMS-TiO2-SiO2The preparation of composite material.
(7): experiment in vitro is prepared into PDMS-TiO2-SiO2Composite material is uniformly applied on float stone, is smeared every two days
Second, aforesaid operations smear (TiO three times repeatedly2Gross mass is 4500mg), and be evenly distributed in glass support plate, it puts
Enter to make in constant temperature and humidity its colloidal sol to solidify 8.2d, i.e. completion PDMS-TiO2-SiO2The preparation of film.It takes out, makes after the completion of solidification
It is spare to be placed in drying in oven later completely with ethyl alcohol and ultrapure water elution with preceding ultrasonic half an hour.Start photocatalysis it
Before, make catalyst dark treatment 1h in dye solution, reaches adsorption equilibrium.Ultraviolet lamp is opened, the AO7 solution of 20mg/L is made
Cycle through PDMS-TiO2-SiO2Film light degradation reaction device, in pH=4, flow velocity 250mLmin-1, solution temperature 35
Under the conditions of DEG C, control unitary variant changes carrier type (three type of the extensive glass fibre of raw material sources, medical stone and float stone
Type carrier is compared), influence of the carrier type to AO7 solution degradation efficiency is probed into, as a result as shown in fig. 7, being to carry with float stone
The degradation efficiency highest that the photo catalysis reactor of body obtains.
Embodiment 6.
(1) 500mg TiO 2 particles are weighed in iodine flask, then are pipetted in 25.00mL dehydrated alcohol to iodine flask, iodine
Measuring bottle is placed on magnetic stirring apparatus, is opened magnetic stirring apparatus, 7.50mL ethyl orthosilicate is pipetted, in the condition quickly stirred
Under, it is added dropwise in iodine flask, is placed on magnetic stirring apparatus and stirs 3h；
(2) after stirring, 5.00mL deionized water is pipetted, is added dropwise in iodine flask, is placed under rapid mixing conditions
30min is stirred on magnetic stirring apparatus；
(3) will iodine flask be placed in ultrasonic cleaner in carry out ultrasound 30min, in ultrasonic procedure by top intake and
Bottom goes out water temperature in water management washer (about 30 DEG C), water level, keeps constant as far as possible；
(4) after ultrasound, 6.00mLPDMS-OH is pipetted, is added dropwise in iodine flask, sets under rapid mixing conditions
In stirring 30min on magnetic stirring apparatus；
(5) iodine flask is placed on magnetic stirring apparatus and is stirred, 5.00mL phosphoric acid is equally added in a manner of being added dropwise and stirs
30min is mixed, i.e. completion PDMS-TiO2-SiO2The preparation of colloidal sol；
(6) by PDMS-TiO2-SiO2Colloidal sol is sealed after being placed in a beaker with preservative film to slow down the evaporation of its solvent, is placed into
In constant temperature and humidity drying case (humidity 60%, 30 DEG C of temperature) after reacted precipitating 72h, bottom white gum substance is obtained, that is, is completed
PDMS-TiO2-SiO2The preparation of composite material.
(7) experiment in vitro is prepared into PDMS-TiO2-SiO2Composite material is uniformly applied on float stone, smears every two days
Secondary, aforesaid operations smear (TiO three times repeatedly2Gross mass is 4500mg), and be evenly distributed in glass support plate, it is put into
Its colloidal sol is set to solidify 8.6d in constant temperature and humidity, i.e. completion PDMS-TiO2-SiO2The preparation of film.It takes out, uses after the completion of solidification
It is preceding ultrasound half an hour, clean with ethyl alcohol and ultrapure water elution later, it is spare to be placed in drying in oven.Before starting photocatalysis,
Make catalyst dark treatment 1h in dye solution, reaches adsorption equilibrium.Ultraviolet lamp is opened, the AO7 solution of 20mg/L is followed
Ring passes through PDMS-TiO2-SiO2Film light degradation reaction device, in pH=4, flow velocity 250mLmin-1, solution temperature be 35 DEG C,
Carrier be float stone under the conditions of, probe into PDMS-TiO2-SiO2The recycling situation of composite photo-catalyst, as a result as shown in figure 8, following
Ring uses five times, and apparent difference does not occur in the degradation situation of AO7 solution concentration, degradation AO7 efficiency remain to reach 90% with
On, illustrate PDMS-TiO2-SiO2The photocatalytic activity of composite photo-catalyst is not shown by the increase that number is recycled
Write decline.
Claims (10)
1. a kind of PDMS-TiO2-SiO2The preparation method of film, it is characterized in that as follows:
(1) float stone, glass fibre or medical stone are cleaned by ultrasonic completely, and are dried in 60 DEG C of baking ovens；
(2) TiO 2 particles are weighed in iodine flask, then pipette mixed in dehydrated alcohol to iodine flask, iodine flask placement
On magnetic stirring apparatus, magnetic stirring apparatus is opened, ethyl orthosilicate is pipetted, under rapid stirring, is added dropwise to iodine
In measuring bottle, it is placed on magnetic stirring apparatus and stirs；
(3) deionized water is added dropwise in iodine flask under rapid mixing conditions, is placed on magnetic stirring apparatus and stirs；
(4) iodine flask is placed in ultrasonic cleaner and carries out ultrasound, be discharged by top water inlet with bottom in ultrasonic procedure
Water temperature, water level in washer are controlled, is kept constant；
(5) after ultrasound, PDMS-OH is added dropwise in iodine flask under rapid mixing conditions, is placed in magnetic stirring apparatus
Upper stirring；
(6) catalyst phosphoric acid is added in a manner of being added dropwise to be stirred, obtains PDMS-TiO2-SiO2Colloidal sol；
(7) by PDMS-TiO2-SiO2Colloidal sol is sealed after being placed in container with preservative film, is placed into reacted in constant temperature and humidity drying case
After precipitating, bottom white gum substance, i.e. PDMS-TiO are obtained2-SiO2Composite material；
(8) experiment in vitro is prepared into PDMS-TiO2-SiO2Composite material is applied on float stone substrate, and certain interval of time smears the
Secondary, aforesaid operations smear certain number repeatedly, and are evenly distributed in glass support plate, and being put into constant temperature and humidity makes its colloidal sol
Solidify a period of time to get PDMS-TiO is arrived2-SiO2Film.
2. preparation method according to claim 1, it is characterized in that the form of TiO 2 particles described in step (2)
Are as follows: anatase titanium dioxide: 70-80%, rutile-type: 20-30%.
3. preparation method according to claim 1, it is characterized in that TiO 2 particles described in step (2) and anhydrous second
The ratio of alcohol is 1:40-50g/mL, and the ratio of TiO 2 particles and ethyl orthosilicate is 1:10-15g/mL；Mixing time is
2-3h。
4. preparation method according to claim 1, it is characterized in that TiO 2 particles and deionization described in step (3)
The ratio of water is 1:6.4-10g/mL, mixing time 10-30min.
5. preparation method according to claim 1 surpasses it is characterized in that ultrasonic time described in step (4) is 10-30min
Water temperature is 25-30 DEG C in sound wave washer.
6. preparation method according to claim 1, it is characterized in that TiO 2 particles and PDMS-OH described in step (5)
Ratio be 1:8-12g/mL, mixing time 10-30min.
7. preparation method according to claim 1, it is characterized in that the ratio of TiO 2 particles described in step (6) and phosphoric acid
Example is 1:6-10g/mL, mixing time 10-30min.
8. preparation method according to claim 1, it is characterized in that constant temperature and humidity drying case described in step (7) imposes a condition
Are as follows: humidity 60%, 25-30 DEG C of temperature；The reaction sedimentation time is 48-72h.
9. preparation method according to claim 1, it is characterized in that interval time described in step (8) is 24-36h, solidification
Time is 7-9d, and smearing number is 3-4 times, smears TiO2Gross mass is 4500mg.
10. according to claim 1 to PDMS-TiO prepared by preparation method described in any claim in 92-SiO2Film exists
Application in fixed bed light degradation reactor.
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| JP2002047032A (en) * | 2000-08-01 | 2002-02-12 | Nippon Sheet Glass Co Ltd | Substrate with photocatalyst membrane and method of producing the same |
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| CN1583248A (en) * | 2004-05-26 | 2005-02-23 | 鞍山市环境保护研究所 | SiO2/TiO2 composite nanometer photocatalysis membrane for treating indoor light pollution air and preparing method thereof |
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